[(η6-p-Cymene)[3-(pyrid-2-yl)-1,2,4,5-tetrazine]chlororuthenium(II)]+, Redox Noninnocence and Dienophile Addition to Coordinated Tetrazine

The bidentate ligand 3-(pyrid-2-yl)-1,2,4,5-tetrazine (TzPy) coordinated in the complex [CyRuCl­(TzPy)]­PF6 ([1]+; Cy = η6-p-cymene) shows noninnocent behavior and can be modified through the addition of dienophiles, vinylferrocene (ViFc) or ethynylferrocene (EthFc). The kinetics and transition-state thermodynamic analysis of the reaction of [1]+ + ViFc found ΔG⧧(298 K) = 67 kJ mol–1, while that of [1]+ + EthFc was ΔG⧧(298 K) = 83 kJ mol–1. The room temperature second-order rate of [1]+ + EthFc, k2 = 1.51(4) × 10–2 M–1 s–1, was 3 orders of magnitude faster than that of EthFc + TzPy, k2 = 1.05(15) × 10–4 M–1 s–1. The [1H2Fc]+ complex was converted to [1Fc]+ by oxidation with oxygen and 3,5-di-tert-butyl-o-quinone, and the molecular structure of [1Fc]+ was determined by single-crystal X-ray diffraction. The title complex [1]+ showed a quasi-reversible reduction in the cyclic voltammogram, and the electrochemical reduction mechanism was determined by UV–vis spectroelectrochemistry (SEC) experiments, as well as supported by density functional theory (DFT) calculations. The dihydropyridazine [1H2Fc]+ and pyridazine [1Fc]+ states of the ligand showed ligand noninnocence similar to that of the parent tetrazine but at a cathodically shifted potential. The dihydropyridazine [1H2Fc]+ showed a mixture of several products; however, upon oxidation, only a single product, [1Fc]+, was formed from the endo addition of the dienophile to [1]+. The electrochemical mechanism of [1Fc]+ was also studied by cyclic voltammetry and UV–vis SEC experiments, as well as supported by DFT calculations.